Iron Chelators Designed to Study Aspects of Siderophore-Mediated Iron(III) Uptake

The investigation of the chemical characteristics of siderophores has been of interest for many years, for both the understanding of their fundamental chemistry and exploiting the design features of these natural compounds for novel applications. Within the present project, the properties of a biomimetic model of the tetradentate siderophore known as the enterobactin linear dimer was investigated, followed by those of the enterobactin linear dimer itself. Both compounds were chemically synthesised, with an overall yield of 52% in four steps for the biomimetic, and 26% in seven-step convergence synthesis for the linear dimer. Investigation of the coordination chemistry, showing both can form complexes with a ligand-to-metal ratios of 3:2 and 1:1 in solution. This was followed up by X-ray diffraction investigations of the ferric-complexes with the periplasmic binding protein CeuE. Both ferric-complexes bound to CeuE in a novel mode, with conserved tyrosine and histidine residues binding directly to the iron(III) centre to complete the octahedral coordination of the metal. Both complexes have a Λ metal centre configuration when bound to CeuE. The dissociation constants of CeuE with ferric-4-LICAM and ferric-linear dimer were determined to be 29.3 ± 11.7 nM and 8.4 ± 4.3 nM for the ferric-4-LICAM and ferric-linear dimer, respectively. In addition, selected applications of siderophores were investigated. Firstly, a synthetic route to a novel hexadentate siderophore mimic possessing a chemical linking group was developed, in an eight-step synthesis with an overall yield of 10.5%. Secondly, the natural hydroxamate siderophore ferricrocin was labelled with an Alexa Fluor® 488 fluorophore. Total internal reflection fluorescence microscopy was used to demonstrate that the resulting conjugate binds to E. coli cells that possess the ferricrocin outer membrane receptor protein FhuA

Gemini-South + FLAMINGOS Demonstration Science: Near-Infrared Spectroscopy of the z=5.77 Quasar SDSS J083643.85+005453.3

We report an infrared 1-1.8 micron (J+H-bands), low-resolution (R=450) spectrogram of the highest-redshift radio-loud quasar currently known, SDSS J083643.85+005453.3, obtained during the spectroscopic commissioning run of the FLAMINGOS multi-object, near-infrared spectrograph at the 8m Gemini-South Observatory. These data show broad emission from both CIV 1549 and CIII] 1909, with strengths comparable to lower-redshift quasar composite spectra. The implication is that there is substantial enrichment of the quasar environment, even at times less than a billion years after the Big Bang. The redshift derived from these features is z = 5.774 +/- 0.003, more accurate and slightly lower than the z = 5.82 reported in the discovery paper based on the partially-absorbed Lyman-alpha emission line. The infrared continuum is significantly redder than lower-redshift quasar composites. Fitting the spectrum from 1.0 to 1.7 microns with a power law f(nu) ~ nu^(-alpha), the derived power law index is alpha = 1.55 compared to the average continuum spectral index = 0.44 derived from the first SDSS composite quasar. Assuming an SMC-like extinction curve, we infer a color excess of E(B-V) = 0.09 +/- 0.01 at the quasar redshift. Only approximately 6% of quasars in the optically-selected Sloan Digital Sky Survey show comparable levels of dust reddening.Comment: 10 pages, 1 figure; to appear in the Astrophysical Journal Letter

Magnetic flux pileup and plasma depletion in Mercury’s subsolar magnetosheath

Measurements from the Fast Imaging Plasma Spectrometer (FIPS) and Magnetometer (MAG) on the MErcury Surface, Space ENvironment, GEochemistry, and Ranging spacecraft during 40 orbits about Mercury are used to characterize the plasma depletion layer just exterior to the planet’s dayside magnetopause. A plasma depletion layer forms at Mercury as a result of piled-up magnetic flux that is draped around the magnetosphere. The low average upstream Alfvénic Mach number (MA ~3–5) in the solar wind at Mercury often results in large-scale plasma depletion in the magnetosheath between the subsolar magnetopause and the bow shock. Flux pileup is observed to occur downstream under both quasi-perpendicular and quasi-parallel shock geometries for all orientations of the interplanetary magnetic field (IMF). Furthermore, little to no plasma depletion is seen during some periods with stable northward IMF. The consistently low value of plasma β, the ratio of plasma pressure to magnetic pressure, at the magnetopause associated with the low average upstream MA is believed to be the cause for the high average reconnection rate at Mercury, reported to be nearly 3 times that observed at Earth. Finally, a characteristic depletion length outward from the subsolar magnetopause of ~300 km is found for Mercury. This value scales among planetary bodies as the average standoff distance of the magnetopause

Ion kinetic properties in Mercury's pre-midnight plasma sheet

With data from the Fast Imaging Plasma Spectrometer sensor on the MErcury Surface, Space ENvironment, GEochemistry, and Ranging spacecraft, we demonstrate that the average distributions for both solar wind and planetary ions in Mercury’s pre-midnight plasma sheet are well-described by hot Maxwell-Boltzmann distributions. Temperatures and densities of the H+ ranges ~1–10 cm3 and ~5–30 MK, respectively, maintain thermal pressures of ~1 nPa. The dominant planetary ion, Na+ abundances with respect to H+ and exhibit mass-proportional ion temperatures, indicative of a reconnection-dominated heating in the magnetosphere. Conversely, planetary ion species are accelerated to similar average energies greater by a factor of ~1.5 than that of H+ acceleration in an electric potential, consistent with the presence of a strong centrifugal acceleration process in Mercury’s magnetosphere

The Velocity Distribution of Pickup He+ Measured at 3.0 AU By Messenger

During its interplanetary trajectory in 2007–2009, the MErcury Surface, Space ENvrionment, GEochemistry, and Ranging (MESSENGER) spacecraft passed through the gravitational focusing cone for interstellar helium multiple times at a heliocentric distance R ≈ 0.3 AU. Observations of He+ interstellar pickup ions made by the Fast Imaging Plasma Spectrometer sensor on MESSENGER during these transits provide a glimpse into the structure of newly formed inner heliospheric pickup-ion distributions. This close to the Sun, these ions are picked up in a nearly radial interplanetary magnetic field. Compared with the near-Earth environment, pickup ions observed near 0.3 AU will not have had sufficient time to be energized substantially. Such an environment results in a nearly pristine velocity distribution function that should depend only on pickup-ion injection velocities (related to the interstellar gas), pitch-angle scattering, and cooling processes. From measured energy-per-charge spectra obtained during multiple spacecraft observational geometries, we have deduced the phase-space density of He+ as a function of magnetic pitch angle. Our measurements are most consistent with a distribution that decreases nearly monotonically with increasing pitch angle, rather than the more commonly modeled isotropic or hemispherically symmetric forms. These results imply that pitch-angle scattering of He+ may not be instantaneous, as is often assumed, and instead may reflect the velocity distribution of initially injected particles. In a slow solar wind stream, we find a parallel-scattering mean free path of λ ∼ 0.1 AU and a He+ production rate of ∼0.05 m−3 s−1 within 0.3 AU

Structure and dynamics of Mercury’s magnetospheric cusp: MESSENGER measurements of protons and planetary ions

The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft has observed the northern magnetospheric cusp of Mercury regularly since the probe was inserted into orbit about the innermost planet in March 2011. Observations from the Fast Imaging Plasma Spectrometer (FIPS) made at altitudes 10 cm−3) that are exceeded only by those observed in the magnetosheath. These high plasma densities are also associated with strong diamagnetic depressions observed by MESSENGER's Magnetometer. Plasma in the cusp may originate from several sources: (1) Direct inflow from the magnetosheath, (2) locally produced planetary photoions and ions sputtered off the surface from solar wind impact and then accelerated upward, and (3) flow of magnetosheath and magnetospheric plasma accelerated from dayside reconnection X-lines. We surveyed 518 cusp passes by MESSENGER, focusing on the spatial distribution, energy spectra, and pitch-angle distributions of protons and Na+-group ions. Of those, we selected 77 cusp passes during which substantial Na+-group ion populations were present for a more detailed analysis. We find that Mercury's cusp is a highly dynamic region, both in spatial extent and plasma composition and energies. From the three-dimensional plasma distributions observed by FIPS, protons with mean energies of 1 keV were found flowing down into the cusp (i.e., source (1) above). The distribution of pitch angles of these protons showed a depletion in the direction away from the surface, indicating that ions within 40° of the magnetic field direction are in the loss cone, lost to the surface rather than being reflected by the magnetic field. In contrast, Na+-group ions show two distinct behaviors depending on their energy. Low-energy (100–300 eV) ions appear to be streaming out of the cusp, showing pitch-angle distributions with a strong component antiparallel to the magnetic field (away from the surface). These ions appear to have been generated in the cusp and accelerated locally (i.e., source (2) above). Higher-energy (≥1 keV) Na+-group ions in the cusp exhibit much larger perpendicular components in their energy distributions. During active times, as judged by frequent, large-amplitude magnetic field fluctuations, many more Na+-group ions are measured at latitudes south of the cusp. In several cases, these Na+-group ions in the dayside magnetosphere are flowing northward toward the cusp. The high mean energy, pitch-angle distributions, and large number of Na+-group ions on dayside magnetospheric field lines are inconsistent with direct transport into the cusp of sputtered ions from the surface or newly photoionized particles. Furthermore, the highest densities and mean energies often occur together with high-amplitude magnetic fluctuations, attributed to flux transfer events along the magnetopause. These results indicate that high-energy Na+-group ions in the cusp are likely formed by ionization of escaping neutral Na in the outer dayside magnetosphere and the magnetosheath followed by acceleration and transport into the cusp by reconnection at the subsolar magnetopause (i.e., source 3 above)

Mercury's Surface Magnetic Field Determined from Proton-Reflection Magnetometry

Solar wind protons observed by the MESSENGER spacecraft in orbit about Mercury exhibit signatures of precipitation loss to Mercury's surface. We apply proton-reflection magnetometry to sense Mercury's surface magnetic field intensity in the planet's northern and southern hemispheres. The results are consistent with a dipole field offset to the north and show that the technique may be used to resolve regional-scale fields at the surface. The proton loss cones indicate persistent ion precipitation to the surface in the northern magnetospheric cusp region and in the southern hemisphere at low nightside latitudes. The latter observation implies that most of the surface in Mercury's southern hemisphere is continuously bombarded by plasma, in contrast with the premise that the global magnetic field largely protects the planetary surface from the solar wind

Transport of Mass and Energy in Mercury’s Plasma Sheet

We examined the transport of mass and energy in Mercury’s plasma sheet (PS) using MESSENGER magnetic field and plasma measurements obtained during 759 PS crossings. Regression analysis of proton density and plasma pressure shows a strong linear relationship. We calculated the polytropic index γ for Mercury’s PS to be ~0.687, indicating that the plasma in the tail PS behaves nonadiabatically as it is transported sunward. Using the average magnetic field intensity of Mercury’s tail lobe as a proxy for magnetotail activity level, we demonstrated that γ is lower during active time periods. A minimum in γ was observed at R ~ 1.4 RM, which coincides with previously observed location of Mercury’s substorm current wedge. We suggest that the nonadiabatic behavior of plasma as it is transported into Mercury’s nearâ tail region is primarily driven by particle precipitation and particle scattering due to large loss cone and particle acceleration effect, respectively.Plain Language SummaryThe transport process of mass and energy within Mercury’s magnetotail remains unexplored until now. The availability of in situ magnetic field and plasma measurements from National Aeronautics and Space Administration’s MErcury Surface, Space ENvironment, GEochemistry, and Ranging spacecraft provides us with the first opportunity to study the thermodynamic properties of particles within sunward convecting closed flux tubes in the plasma sheet. In this study, we study how mass and energy are transported in Mercury’s magnetotail by investigating the relationship between the thermal pressure and number density of the plasma in Mercury’s plasma sheet given by the equation of state in magnetohydrodynamics theory. We determined, for the first time, that the plasma behaves nonadiabatically as it is transported sunward toward Mercury. We suggest that precipitation of particles due to Mercury’s large loss cone and demagnetization of particles due to finite gyroradius effect contributes to this nonadiabatic behavior of plasma in the plasma sheet. Our results have major implications in our understanding of particle sources and sinks mechanisms in Mercury’s magnetotail.Key PointsWe calculated the value of polytropic index γ for Mercury’s plasma sheet to be ~0.687, which is smaller than 5/3 (adiabatic)Nonadiabatic plasma behavior is driven by ion precipitation and ion demagnetization due to large loss cone and finite gyroradius effectWe demonstrated that γ is lower during active time and determined a relationship between γ and the location of flow breaking regionPeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/147033/1/grl58293_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/147033/2/grl58293.pd

Plasma distribution in Mercury’s magnetosphere derived from MESSENGER Magnetometer and Fast Imaging Plasma Spectrometer observations

We assess the statistical spatial distribution of plasma in Mercury’s magnetosphere from observations of magnetic pressure deficits and plasma characteristics by the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft. The statistical distributions of proton flux and pressure were derived from 10 months of Fast Imaging Plasma Spectrometer (FIPS) observations obtained during the orbital phase of the MESSENGER mission. The Magnetometer-derived pressure distributions compare favorably with those deduced from the FIPS observations at locations where depressions in the magnetic field associated with the presence of enhanced plasma pressures are discernible in the Magnetometer data. The magnitudes of the magnetic pressure deficit and the plasma pressure agree on average, although the two measures of plasma pressure may deviate for individual events by as much as a factor of ~3. The FIPS distributions provide better statistics in regions where the plasma is more tenuous and reveal an enhanced plasma population near the magnetopause flanks resulting from direct entry of magnetosheath plasma into the low-latitude boundary layer of the magnetosphere. The plasma observations also exhibit a pronounced north-south asymmetry on the nightside, with markedly lower fluxes at low altitudes in the northern hemisphere than at higher altitudes in the south on the same field line. This asymmetry is consistent with particle loss to the southern hemisphere surface during bounce motion in Mercury’s offset dipole magnetic field

Solar Wind Alpha Particles and Heavy Ions in the Inner Heliosphere Observed with MESSENGER

The Fast Imaging Plasma Spectrometer (FIPS) on the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft has made the first in situ measurements of solar wind plasma in the inner heliosphere since the Helios 1 and 2 spacecraft in the 1980s. Although the core of the solar wind velocity distribution is obstructed by the spacecraft sunshade, a data analysis technique has been developed that recovers both bulk and thermal speeds to 10% accuracy and provides the first measurements of solar wind heavy ions (mass per charge >2 amu/e) at heliocentric distances within 0.5 AU. Solar wind alpha particles and heavy ions appear to have similar mean flow speeds at values greater than that of the protons by approximately 70% of the Alfvén speed. From an examination of the thermal properties of alpha particles and heavier solar wind ions, we find a ratio of the temperature of alpha particles to that of protons nearly twice that of previously reported Helios observations, though still within the limits of excessive heating of heavy ions observed spectroscopically close to the Sun. Furthermore, examination of typical magnetic power spectra at the orbits of MESSENGER and at 1 AU reveals the lack of a strong signature of local resonant ion heating, implying that a majority of heavy ion heating could occur close to the Sun. These results demonstrate that the solar wind at plus or minus 0.3 AU is a blend of the effects of wave–particle interactions occurring in both the solar corona and the heliosphere